EP0072353B1 - Lentilles de contact colorées et procédé pour leur fabrication - Google Patents

Lentilles de contact colorées et procédé pour leur fabrication Download PDF

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Publication number
EP0072353B1
EP0072353B1 EP82810330A EP82810330A EP0072353B1 EP 0072353 B1 EP0072353 B1 EP 0072353B1 EP 82810330 A EP82810330 A EP 82810330A EP 82810330 A EP82810330 A EP 82810330A EP 0072353 B1 EP0072353 B1 EP 0072353B1
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Prior art keywords
lens
dye
reactive
lenses
contact lens
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EP0072353A3 (en
EP0072353A2 (fr
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Kai Chiang Su
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Novartis AG
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Agripat SA
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/008—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using reactive dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/021—Lenses; Lens systems ; Methods of designing lenses with pattern for identification or with cosmetic or therapeutic effects

Definitions

  • the invention relates to tinted or slightly colored contact lenses and processes for their production.
  • the invention relates to contact lenses which contain polymeric lens materials in which reactive dyes have been covalently bound to monomer units of the polymer backbone.
  • the invention is of particular interest in the field of so-called hydrophilic or "soft" contact lenses, which are commonly referred to as hydrogel lenses.
  • Many of the known methods for tinting or coloring plastic materials are unsuitable for the practical coloring of contact lenses, in particular of hydrophilic contact lenses.
  • those methods in which a colorant is dispersed in a plastic by dissolving or dispersing a dye or pigment in a monomer precursor or in the polymer matrix cannot be used to achieve satisfactory water-absorbable materials. This is because water causes the coloring agent to migrate within the plastic material and leach the dye therefrom.
  • a coloring agent is adhered to the surface of the plastic.
  • This method is also unsuitable for coloring water-absorbent plastics, such as those used for the production of hydrophilic contact lenses. If a plastic material colored by this process is allowed to swell in water, the applied layer of the coloring agent does not swell as much as the plastic itself. The coloring agent therefore separates from the surface of the plastic.
  • a simple transfer dyeing method does not prevent the leaching problem and is always limited by the amount of physical adhesion of the dye to the surface.
  • water-soluble dyes are also unsatisfactory for the production of, in particular, soft contact lenses.
  • Water soluble dyes are leached out during repeated thermal stabilization treatments.
  • water-soluble dyes could stain the eye tissue in long-term contact with the eye. In this way, the method described in American Journal of Optometry and Physiological Optics, Volume 54, pp. 160-164 (1977) "Methods of Tinting Soflens® Contact Lenses" would not solve the problem of making useful tinted soft contact lenses.
  • Common hard contact lenses which are generally made from formulations containing methyl methacrylate as the main comonomer, generally have a diameter that is less than the diameter of the cornea of the eye. It is therefore possible to use a lens that is colored over its entire extent. In contrast, soft contact lenses very often have a diameter that is larger than that of the cornea. For this reason, an evenly colored soft contact lens would stand out strongly against the white sclera of the eye. In order to make a neutral looking contact lens, it would therefore be necessary for it to have a colored central surface and a clear outer circumference.
  • U.S. Patent 4,252,421 describes a method of making soft contact lenses which have a tinted central core and an outer lens element which is usually clear.
  • the colored central core is made from a tinted button, which in turn is polymerized from a mixture of monomers containing a dye as a comonomer.
  • a dye as a comonomer.
  • the water-insoluble dye or dyes are part of the basic structure of the polymer.
  • a water-insoluble dye can be added to the comonomer mixture and this combination polymerized, whereby the dye is included in the polymer matrix. Because of the insolubility of the dye it is not bled or drained from the polymerized button. Two methods of making the contact lens are also described.
  • the first method is to polymerize the tinted button, insert the tinted button into a mold, and pour a hydrogel-comomer mixture around the tinted button and polymerize this mixture.
  • An alternative method of forming the lens is to first polymerize the clear outer button and then form a central opening through the button. The comonomer mixture containing the dye is then inserted into the opening and polymerized.
  • US Pat. No. 4,157,892 describes a process for coloring water-absorbent plastic which has four stages.
  • the first step is to make a coupler monomer or polymer.
  • a polymerization radical is introduced into a coupler to achieve a polymerizable coupler monomer from which a coupler polymer can be made.
  • Each of the couplers obtained in the first step is then copolymerized or polymerized with a water-absorbent plastic in the form of a monomer or a polymer in the presence of a polymerization initiator to form a water-absorbent plastic that can be colored.
  • the material so produced is formed into an intermediate product having the same dimensions as that of the desired end product, such as a water-absorbing contact lens.
  • the intermediate is colored by immersing the lens in an aqueous solution of a diazonium double salt, which acts as a developer. Immersion is carried out for as long as is necessary to cause the intermediate to swell, allowing the diazo component to penetrate the plastic. The solution is then adjusted to an optimal pH to effect a coupling reaction and to allow the azo dye to develop color in the final product.
  • Partially colored intermediates can be obtained by applying ultraviolet radiation to the portions of the plastic that are not to be colored, thereby destroying the diazo components in these portions.
  • This method also has the disadvantage that it is quite complicated in terms of procedure.
  • the procedure for producing the material in which the color is to be developed last must be carried out in a number of different stages and care must be taken to ensure that the azo dye does not develop prematurely in the lens material.
  • the azo dye precursor is dispersed over the entire lens material, which can lead to differences in color intensity depending on the thickness of the lens material.
  • To provide colored lenses for a variety of prescriptions it is also necessary for the distributor to have a large inventory available. It can also be seen that this procedure is only suitable for use with a specially prepared lens material containing a coupler. It is therefore not possible to use the method described in U.S. Patent No. 4,157,892 with conventional hydrophilic lens materials currently in use.
  • the use of couplers of the type described in this reference can result in poorer quality polymer materials compared to materials currently used for this purpose.
  • GB-A-1 004 424 discloses those dyes which are suitable for dyeing contact lenses and which are customarily used for dyeing cellulose textile materials. This teaching is substantiated by the note that good results can be achieved with azo, vat and reactive dyes.
  • the only reactive dye specifically mentioned is Cibacron Blue 3G or Procion Brilliant Blue RS. At most, this reactive dye can form a sulfonic acid ester bond with cellulose.
  • an ether bond such a sulfonic acid ester bond is not inert to hydrolytic influences, e.g. B. by sterilization solutions.
  • GB-A 1 004 424 does not indicate that temperatures of up to 40 ° C. are not only sufficient, but also advantageous, for the coloring of contact lenses. Dyes such as the proposed Cibacron Blue 3G actually do not normally bind to contact lenses at temperatures up to 40 ° C, but only at higher temperatures. At temperatures up to 40 ° C there is practically no decomposition or deformation of the hydrogel substrate, while at higher temperatures such damage to lenses can occur.
  • An object of the present invention is therefore to avoid the problems that arise with the methods of the prior art.
  • Another object of the present invention is to provide a method for coloring lenses that can be kept in inventory in an untinted condition or that are already available on the market and / or have been prescribed to the patient.
  • Further objects of the invention include providing a method of making a contact lens that appears completely natural when worn on the eye, i.e. H. of lenses with a central colored part covering the cornea and clear edges over the part of the lens covering the sclera. Another object of the invention is to provide contact lenses that retain color over long periods of time and repeated chemical and / or heat sterilization treatments. Another object of the invention is to manufacture contact lenses with a wide range of colors and color combinations by simple mechanical procedures.
  • An object of the invention is a contact lens, at least part of which is colored, which contains a copolymeric hydrogel material which contains hydroxyl, amino, amido or mercapto groups, characterized in that at least one reactive dye of the formula I or II by ether -, Thioether-, Amino- or Amido groups is covalently bound from the outside to the polymer structure.
  • a variety of polymers are suitable for use in the manufacture of the new lenses.
  • the only requirement is that the monomers contain at least one of the functional groups that are suitable for reaction with a reactive dye, either before or after the polymerization of the monomers to form the polymer.
  • composition of the lens material itself can vary within wide ranges, the only requirement is the presence of at least one component in the monomer mixture which provides the polymer with the required exoskeletal functional groups.
  • Hydroxyalkyl esters of polymerizable unsaturated acids are particularly suitable as monomers for this purpose.
  • esters hydroxyethyl methacrylate (HEMA) has been widely used; Lenses made from such materials are described, for example, in U.S. Patents 2,976,576 and Re 27,401.
  • any polymeric material which is suitable for use in the manufacture of a contact lens also for the preparation of be it f indungsgefflessen tinted lenses used with the proviso that at least one of the monomeric components which form the material, the exoskeletal functional Contains group that can react with the reactive dye molecule. Therefore, the present invention can be applied to a variety of known polymeric lens materials. This also provides the ability to manufacture tinted contact lenses in accordance with the invention from the wide range of materials already available as well as new contact lens materials that have yet to be developed or placed on the market.
  • the following monomeric materials can serve as typical examples of comonomers that can be used with monomers that provide the desired functional groups: acrylic acid and methacrylic acid; Alkyl and cycloalkyl acrylates and methacrylates; N- (1,1-dimethyl-3-oxobutyl) acrylamide; and heterocyclic N-vinyl compounds containing a carbonyl function adjacent to the nitrogen in the ring, especially N-vinyl lactams such as N-vinyl pyrrolidone.
  • one or more crosslinking agents can be used to give a polymeric material with optimal properties. Examples of such crosslinking agents include trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate (EDMA) and diethylene glycol bis-allyl carbonate.
  • ether bond-forming reactive dyes Useful reactive dyes according to the invention are commonly referred to as "ether bond-forming reactive dyes" because the reactive group or groups of this known class of dyes react with cellulose to form an ether bond, as opposed to, for example, an ester bond.
  • ether bond-forming reactive dyes Such reactive dyes that form ether bonds are generally described in FIBER-REACTIVE DYES, Chapter VI by W.F. Beech, SAF, International Inc., New York (1970).
  • This class of reactive dyes with hydroxyl, amino, amido or mercapto groups present in the hydrogel-polymer network of contact lens materials are believed to react primarily by nucleophilic addition to form a covalent bond therewith.
  • a large number of commercially available dyes which are reactive via the nucleophilic substitution are suitable for use in the production of the contact lenses according to the invention.
  • practically any desired shade or tint can be achieved by using a special reactive dye or a combination of reactive dyes.
  • dyes which contain an active double bond which is suitable for addition to the functional group on the outside of the polymer structure can be used according to the invention.
  • an exoskeletal bond activated by a bridge member such as a -S0 2 -, -SO or -CO group, is particularly suitable for use in accordance with the invention.
  • Dyes with functional groups which can undergo addition reactions with exoskeletal double bonds of the polymer can be used in the same way.
  • reactive dyes which contain vinylsulfone precursors, such as ⁇ -sulfatoethylsulfonyl, ⁇ -sulfateethylsulfonamido, ⁇ -hydroxyethylsulfonyl and ⁇ -hydroxyethylsulfonamido Substituents, as well as suitable derivatives thereof, dyes, the acryloylamino-, ⁇ - Contain chloropropionylamino and p-sulfatopropionylamino groups and related reactive groups; Dyes containing ß-phenylsulfonylpropionylamino groups; Dyes containing ⁇ -sulfato or ⁇ -chloroethylsulfamoyl groups; Chloroacetyl dyes; ⁇ -bromoacryloyl dyes; as well as many other reactive dye
  • dyes which contain more than one reactive group which is suitable for forming a covalent bond by nucleophilic addition with hydroxyl, amino, amido or mercapto groups which are present in the hydrogel polymer network of the contact lens materials falls within the scope of the invention are.
  • the radical D can preferably be the radical of an azo, phthalocyanine, azomethine, nitro or anthraquinone dye.
  • the reactive dyes of the formula II eliminate HY in the reaction media, as a result of which intermediate products of the formula I are formed which then react by nucleophilic addition.
  • the divalent group -R- is preferably bonded directly to an aromatic nuclear carbon of D or to it via an aliphatic group such as an alkylene group, e.g. B. a lower alkylene group. Most preferably, -R- is attached directly to a core carbon atom of D.
  • Suitable divalent groups R include ⁇ CO ⁇ , ⁇ SO 2 -, ⁇ SO ⁇ , ⁇ NHCO ⁇ , ⁇ NHSO 2 -, -S0 2 NH- and the like. Most preferably R has the meaning of ⁇ SO 2 -, -S0 2 HN-, -CO- or -NHCO-.
  • X is halogen, it is most preferably chlorine or bromine.
  • Suitable leaving groups Y include ⁇ Cl, -Br, -OH, di-lower alkylamino, -S0 2 -phenyl, -OS0 3 -Z + , where Z + is a cation, -0SO 3 R, or ⁇ OSO 2 R 1 , wherein R 1 is in each case alkyl, aryl, aralkyl or alkaryl.
  • R 1 is alkyl, it is advantageously alkyl having 1 to 6 carbon atoms, preferably alkyl having 1 to 4 carbon atoms.
  • R 1 is aryl, it is preferably phenyl or naphthyl.
  • R 1 is alkaryl it is preferably lower alkyl substituted phenyl such as tolyl or xylyl and when R 1 is aralkyl it is preferably phenyl lower alkyl such as benzyl or phenethyl.
  • the reactive dyes of formula I and 11 form a covalent bond with the hydroxyl, amino, amido or mercapto groups present in a hydrogel polymer network in an aqueous medium with a pH of 9 or greater and a temperature up to 40 ° C.
  • These dyes of the formula I or II are suitable for coloring hydrogel contact lenses without substantial decomposition or deformation of the hydrogel substrate due to the mild reaction conditions.
  • the invention provides new tinted lenses with exceptional color fastness and color uniformity.
  • the dye can be applied to both surfaces of a lens or only to one surface.
  • the method can, for example, also be applied to the application of identifying features on lenses, such as for displaying the concave or convex surface of a flexible lens.
  • tinting or coloring is effected by contacting one or both surfaces of the lenses with an aqueous solution of the dye, inner parts of the lens are also tinted or colored to a certain extent, due to the diffusion of the dye during the reaction time.
  • the formation of a covalent bond between the lens material and the reactive dye is accomplished by simply contacting the dye formulation, such as a mildly basic aqueous solution, with the lens material until the reaction is complete. If both surfaces of a lens are to be colored, the lens is brought into contact with a formulation of the reactive dye on both surfaces. The tone of the color is controlled by the contact time with the dye formulation and by the reactivity of the dye with the lens surface. If it is desired to apply the dye only to a surface or to a specific part of the surface, the lens produced can be placed in a fastener or mold, and the formulation of the reactive dye is applied only to a specific part or parts of the lens surface applied. In view of the complicated methods generally used hitherto, this simple mechanical procedure for tinting contact lenses is a great advantage.
  • the dye formulation such as a mildly basic aqueous solution
  • the lens in the colored part has a light transmittance of 90% or less in the desired visible color range and that it is substantially free of opaque in the colored part.
  • the unreacted dye can be removed using a suitable solvent.
  • solvent for extraction or rinsing naturally depends on the solubility of the specific dye. Low alcohols such as methanol are suitable solvents for the majority of the dyes currently used.
  • the tinted lens is freed from traces of the solvent, for example by boiling in distilled water.
  • the lenses according to the invention have considerable color fastness to all types of sterilization treatments which are usually used for contact lenses, such as chemical, enzymatic and heat sterilization.
  • the coloring material is applied directly to the surface or surfaces of the lenses, the color tone is independent of the thickness of the lenses. This is in marked contrast to lenses made from plastic buttons in which the pigment is incorporated into the polymer matrix, since in this case the intensity of the color tone depends directly on the thickness of the lens. This applies, for example, to the contact lenses that are manufactured in accordance with US Pat. No. 4,157,872.
  • the procedure according to the invention enables the coloring material to be introduced at any time during the production of the colored lenses, it is possible to tint conventional clear lenses after a special regulation has been met. Thus, it is not necessary to keep a large stock of pre-colored lenses, which is a major disadvantage of numerous known methods for producing tinted lenses.
  • the color can be introduced as a final stage before delivery to the patient. Alternatively, can be prescribed in advance bene lenses are tinted later depending on the needs of the wearer for the customer. Since the range of polymeric materials suitable for use according to the invention is sufficiently wide to encompass practically all lens materials currently in use, the procedure according to the invention can be used almost universally.
  • Another advantage of the method according to the invention is the extreme reduction in the cost of production for the contact lenses according to the invention, in comparison with known methods for producing lenses which have at least one central part which has been colored.
  • Suitable reactive dyes are readily available, and the easy application of these dyes to the lens materials eliminates the need to use complex polymerization processes or equipment.
  • Another advantage of the lenses according to the invention is that most of the dyes used for tinting to absorb ultraviolet radiation, in particular of the wavelengths which have been found to be harmful to the eye, e.g. B. shown in Optical Management. "Ultraviolet Radiation and the Ocular Media •, January 1981, pages 21-33. In particular, it has been reported that ultraviolet radiation may be directly related to the development of cataracts.
  • a storage solution that is stable for at least 5 weeks is made by dissolving 0.1 g of a dye having the formula in 10 ml of 0.001 m HCl solution.
  • a clear HEMA lens is soaked in 1.0 m sodium carbonate solution. The lens softened with sodium carbonate is then placed in 0.11 ml of the storage solution. 4 ml of 1.0 M sodium carbonate solution is then added and the lens is left in the solution for 53 minutes.
  • the tinted lens is then extracted with methanol as the solvent in a solvent extraction device until no more dye molecules are leached out. This can easily be determined, for example, by a spectrophotometer. After the extraction process, the tinted lens is boiled in boiling water for 1 hour to remove any traces of methanol. Then the tinted lens is stored in a salt buffer solution.
  • the transmission of the tinted lens at a wavelength of 600 nm is 68%.
  • a storage solution that is stable for at least 3 weeks is prepared by dissolving 0.1 g of a dye of the formula in 10 ml of 0.001 m HCl solution.
  • the lens which has been soaked in 1.0 M sodium carbonate solution for 10 minutes, is placed in 1 ml of the storage solution. 4 ml of 1.0 m sodium carbonate solution are added and the lens is soaked for the desired time.
  • the procedures for washing, extracting and rinsing the lens are the same as in Example 1.
  • the transmission of the tinted lenses at a wavelength of 670 nm is 80% and 70% for 2 and 4 hours of soaking.
  • the lens which was immersed in 1.0 M sodium carbonate solution for 10 min, is used in 0.18 ml A, 0.12 ml B and 0.2 ml C storage solutions. 1 ml of 1.0 M sodium carbonate solution is then added and it is left to stand for 1 hour.
  • the transmission of the tinted lens at wavelengths of 400, 490 and 605 nm is 45%, 51% and 60%, respectively.
  • the lens which was soaked in 1.0 M sodium carbonate for 10 minutes, is used in 0.18 ml of solution C and 0.12 ml of solution B, prepared according to Example 3. Then 1 ml of 1.0 M sodium carbonate solution is added and the lens is soaked in the solution for 30 minutes.
  • the transmission of the tinted lens at wavelengths of 580 and 385 nm is 64% and 58%, respectively.
  • the tinting process is the same as in Examples 1 to 4. The only difference is that the clear lens sits in a fixture. A suitable dye solution is then placed in a mold instead of immersing the lens in the dye solution. Only the surface to be colored is then in contact with the. Brought dye solution. The final stages of the procedure are the same as in Example 1.
  • the lens which was soaked in 1.0 m sodium carbonate for 10 minutes, is placed on the dome.
  • the container part of the fastening device is attached and clamped.
  • the container is filled with the desired dye concentration and with sodium carbonate solution.
  • the solution is left in contact with the lens until the desired shade is achieved.
  • the container is rinsed with water until all traces of the dye solution have been removed.
  • the lens is then removed from the fastening device.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • General Physics & Mathematics (AREA)
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Claims (13)

1. Lentille de contact dont au moins une partie est colorée, contenant une matière d'hydrogel copolymère, qui contient des groupes hydroxyle, amino, amido, ou mercapto, caractérisée en ce qu'au moins un colorant réactif de formule générale
Figure imgb0028
ou
Figure imgb0029
où
D est le radical d'un colorant organique ;
R est un groupe électrophile organique bivalent qui convient pour provoquer un enlèvement d'électrons des atomes de carbone dans les groupes C = CH2 ou CH-ÇH2 de formules I et Il et ainsi pour les activer ;
X est un hydrogène ou un halogène et
Y est un groupe sortant,

est lié de façon covalente de l'extérieur sur l'ossature de polymère par des groupes éther, thioéther, amino ou amido.
2. Lentille de contact selon la revendication 1, où le radical colorant réactif qui est lié à l'hydrogel copolymère présente les formules
Figure imgb0030
ou
Figure imgb0031
où D, R et X ont les significations données dans la revendication 1.
3. Lentille de contact selon la revendication 2, où D est le radical d'un colorant azo, phthalocyanine, azométhine, nitro ou anthraquinone.
4. Lentille de contact selon la revendication 2, où R est -CO-, ―SO2―, -SO-, -NHCO- ou -NHS02.
5. Lentille de contact selon la revendication 1, contenant une partie centrale colorée et un bord annulaire clair.
6. Procédé de préparation d'une lentille de contact selon les revendications 1 à 5, caractérisé en ce que la réaction de la matière de lentille avec au moins un colorant réactif de formule 1 ou Il est conduite à une température allant jusqu'à 40 °C puis en ce qu'on enlève de la matière de lentille le colorant n'ayant pas réagi.
7. Procédé selon la revendication 6, où la réaction est conduite en milieu aqueux avec un pH d'au moins 9.
8. Procédé selon la revendication 6, où la matière de lentille se présente sous.la forme d'une lentille de contact.
9. Procédé selon la revendication 6, où le colorant réactif n'est déposé que sur une partie de la lentille.
10. Procédé selon la revendication 6, dans lequel le colorant réactif présente la formule
Figure imgb0032
ou
Figure imgb0033
où D, R, X et Y ont les significations données dans la revendication 1.
11. Procédé selon la revendication 10, où D est le radical d'un colorant azo, phthalocyanine, azométhine, nitro ou anthraquinone.
12. Procédé selon la revendication 10, où R est -CO-, ―SO2―, -NHCO- ou ―NHSO2―.
13. Procédé selon la revendication 10, où le groupe sortant Y représente CI, Br, OH, dialcoylamino, S02-phényle, OSO3 -Z+, où Z+ est un cation, OSO3R1 ou OSO2R1, où R1 représente un alcoyle, aryle, aralcoyle ou alcaryle.
EP82810330A 1981-08-12 1982-08-06 Lentilles de contact colorées et procédé pour leur fabrication Expired EP0072353B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82810330T ATE26555T1 (de) 1981-08-12 1982-08-06 Getoente kontaktlinsen und verfahren zu deren herstellung.

Applications Claiming Priority (2)

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US29232581A 1981-08-12 1981-08-12
US292325 1981-08-12

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EP0072353A2 EP0072353A2 (fr) 1983-02-16
EP0072353A3 EP0072353A3 (en) 1983-07-20
EP0072353B1 true EP0072353B1 (fr) 1987-04-15

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JP (2) JPS5846319A (fr)
AT (1) ATE26555T1 (fr)
AU (1) AU555473B2 (fr)
BR (1) BR8204719A (fr)
CA (1) CA1190708A (fr)
DE (1) DE3276056D1 (fr)
DK (1) DK159723C (fr)
ES (1) ES8305504A1 (fr)
FI (1) FI78019C (fr)
GB (1) GB2105061B (fr)
GR (1) GR76890B (fr)
HK (1) HK16489A (fr)
IE (1) IE54081B1 (fr)
IL (1) IL66506A (fr)
MX (1) MX159763A (fr)
NO (1) NO165818C (fr)
NZ (1) NZ201561A (fr)
PT (1) PT75373B (fr)
SG (1) SG56688G (fr)
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Publication number Priority date Publication date Assignee Title
CA1233302A (fr) * 1983-04-11 1988-03-01 Miles W. Press Articles en plastique hydrogel colores et methode de coloration
US4891046A (en) * 1984-03-15 1990-01-02 Coopervision, Inc. Tinted contact lens and method for preparation with dichlorotriazine reactive dye
IL77453A (en) * 1985-01-04 1992-09-06 Schering Corp Colored contact lenses and method for making same
US4733959A (en) * 1985-05-01 1988-03-29 Optatint, Inc. Apparatus and method for tinting hydrophilic contact lenses
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DK159723C (da) 1991-04-29
JPS5846319A (ja) 1983-03-17
GB2105061A (en) 1983-03-16
IE821937L (en) 1983-02-12
DK159723B (da) 1990-11-26
FI78019B (fi) 1989-02-28
AU8706282A (en) 1983-05-12
CA1190708A (fr) 1985-07-23
MX159763A (es) 1989-08-17
NO165818B (no) 1991-01-02
FI78019C (fi) 1989-06-12
FI822771A0 (fi) 1982-08-09
EP0072353A3 (en) 1983-07-20
GB2105061B (en) 1985-09-18
ES514901A0 (es) 1983-04-16
FI822771L (fi) 1983-02-13
JPH0263212B2 (fr) 1990-12-27
BR8204719A (pt) 1983-08-02
JPH0643402A (ja) 1994-02-18
ES8305504A1 (es) 1983-04-16
NO165818C (no) 1991-04-10
IL66506A0 (en) 1982-12-31
EP0072353A2 (fr) 1983-02-16
GR76890B (fr) 1984-09-04
IE54081B1 (en) 1989-06-07
NO822738L (no) 1983-02-14
NZ201561A (en) 1985-08-16
ATE26555T1 (de) 1987-05-15
SG56688G (en) 1989-05-26
DK361382A (da) 1983-02-13
DE3276056D1 (en) 1987-05-21
PT75373B (en) 1986-06-18
JPH0664265B2 (ja) 1994-08-22
HK16489A (en) 1989-03-03
AU555473B2 (en) 1986-09-25
PT75373A (en) 1982-09-01
IL66506A (en) 1986-07-31
ZA825803B (en) 1983-06-29

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